Trifluoromethylated diphenyl ether sulfonic acids



Patented Aug. 18, 1953 UNITED TRIFLUOROMETHYLATED DIPHENYL ETHERSULFONIC ACIDS Henry Martin, Schaffhausen, Switzerland, as-

signor to Variapat A. G., Basel, Switzerland No Drawing. ApplicationApril 24, 1951, Serial No. 222,738. In Switzerland April 29, 1950 6Claims.

It has been found that certain colourless and water-solublecondensation-products of the arcmatic or heterocyclic series, containingtrifluoromethyl groups have outstanding properties for the permanentprotection of all kinds of textiles, but especially wool and also furs,feathers, hides, hairs and the like as well as articles made of suchproducts against attack by textile pests.

Said condensation-products of the aromatic or heterocyclic seriescontaining trifluoromethyl groups may be obtained by interaction ofacylating agents with aromatic or heterocyclic aminosulphonic-acidscontaining an exchangeable hydrogen atom at the nitrogen atom, wherebythe components of the reaction have to be so chosen that the end productcontains at least one trifiuoromethyl group, a sulphonic-acid-group anda diphenyl-radical or a diphenyloxide-, diphenylsulphide-,dipheny1sulphoxide-, diphenylsulphone-, diphenylmethane-,diphenylcarbamide-,

stilbene-radical respectively.

As acylating agents for these aminosulphonicacids, sulphonic-acids aswell as carboxylic-acids and their derivatives capable of reaction maybe used. The term carboxylic-acids and their derivatives capable ofreaction comprehends as well monobasic as polybasic carboxylic-acids.Besides these normal acids and their derivatives the various derivativesof the carbonic-acid or thiocarbonic-acid and of the cyanuric-acid areeminently suited.

The acylation of the above named aromatic or heterocyclicaminosulphonic-acids having free amino-groups may be accomplished withacids of the aliphatic-, araliphatic-, alicyclic-, aromaticandheterocyclic-series. It is obvious that their functional derivativeslike halides, esters, anhydrides and the like too may be used in thepresent process, as it is commonly known in the acylating technique.

For example the following carboxylic-acids or sulphonic-acids may bementioned:

Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid,palmkernel oil fatty acid, oleic acid, phenylacetic acid,p-chlorophenyl-acetic acid, 3,4-dichlorophenyl-acetic acid, cinnamicacid, p-chloro cinnamic acid, hydrocinnamic acid, phenoxy acetic acid,halogen substituted and alkylsubstituted phenoxy-a-cetic acids,hexahydrobenzoic acid, p-tolylic acid, benzoic acid, 3,4-dimethyl-benzoic acid, 4-chlorobenzoic acid, 3,4- dichlorobenzoic acidor 2,4-dichlorobenzoic acid, 2-ch1orobenzoic acid, malonic acid,succinic acid, adipic acid, phthalic acid, sulphob o c acid,trifiuoromethyl benzene carboxylic acid, d1-

phenylether-4-carboxylic acid, 2',4-dichloro-1,l'-d1iphenylether-4'-carboxylic acid, 2,4-dichloro-1,1-diphenylether-4-carboxylic acid, 4-ch1oro-1,1-diphenylether-4'-carboxylic acid, 2-chloro-1,1-diphenylether-4'-carboxylic acid, diphenylene oxide-3-carboxylicacid, 2-ch1oroquinolinel-carboxylic acid, toluenesulphonic acid, 4-chlorobenzene-sulphonic acid, 3,4-dichlorobenzenesulphonic acid,trifluoromethylbenzene-sulphonic acid,1-trifluoromethyl-4-chlorobenzene- 3-sulphom'c acid,diphenyletherll-sulphonic acid, 4-ch1oro-Ll -diphenylether-4'-sulphonicacid.

Derivatives of carbonicand thiocarbonic acid which may be condensed withthe aromatic or heterocyclic aminosulphonic acids are halides,-

esters, amides, imides or anhydrides of said acids, whereby carbonicacid halides or thiocarbonic acid halides are carbonyl-chloride,thiocarbonylchloride, aliphatic, araliphatic, aliphatic-aromatic,aromatic and heterocyclic carbamic acid chlorides but also aliphatic,aromatic and araliphatic chlorocarbonic acid esters. There have provedparticularly valuable trifluoromethylsubstituted but also halogen and/oralkyl substituted aromatic carbamic acid chlorides.

The condensation products in question may also be obtained with otherderivatives of carbamic acid; for example by addition of the carbamicacid anhydrides or of substances delivering such derivatives of carbamicacid. Similar substances are formed by addition of aromatic orheterocyclic carbamic acid chloride sulphonic acids or isocyanatesulphonic acids to suitable aromatic or heterocyclic amines. Moreoverthe addition of saturated or unsaturated aliphatic, araliphatic oraromatic isothiocyanic acid esters and especially of halogen substitutedoils of mustard to aromatic or heterocyclicaminosulphonic acids giveswatersoluble compounds of high interest. But other methods as forexample treatment of carbon disulphide with said aminosulphonic acids inthe presence of suitable catalysts, for example hydrogenperoxide orsulphur leads to thiocarbamide derivatives. By warming, melting orheating in suitable solvents or suspension media of the aminosulfonicacids with urea or thiocarbamide or urethanes with splitting ofE ammoniaor alcohol, similar products may be obtained.

Another method for preparing said watersoluble products of condensationwhich contain trifluoromethyl-groups, which works in two steps, consistin reacting aromatic or heterocyclic amines or their sulphonic acidswith carbonic 3 acid derivatives capable of double reaction, as forexample halogenated carbonic acid esters, whereby said carbonic acidderivatives react at first only partially in one step whereupon theseprimary products of condensation are further reacted with e. g. aminessubstituted by trifluoromethyl-groups to form the desired products ofcondensation containing trifluoromethylgroups. On the other hand one mayalso start with amines or aminosulphonic acids containingtrifluoromethyl-groups which are reacted with carbonic acid derivativescapable of double reaction e. g. halogenated carbonic acid phenylesterin order to obtain the primary trifluoromethylgroup containing productsof condensae tion which are then reacted with substituted amines to givethe corresponding products of condensation containingtrifiuoromethylgroups.

Sulphonic acids with surprisingly good properties may also be obtainedby aftertreatment of the finished difiicultly soluble or insoluble carbamides or thiocarbamides containin at least one trifiuoromethylgroupwith a sulphonating agent.

The desired carbamide derivatives may also be obtained by condensationof alkylor arylcarboxylic acid azides or N'halogen carbonic acid amideswith aminosulphonic acids with development of nitrogen or splitting ofihydrohalide. In all these methods the substitution of the componentsmust be such that the end product contains at least onetrifiuoromethylgroup. Said group may be in only one or in both of thecomponents of reaction.

The carbamic acid halides, halogen carbonic acid esters, isocyanic acidesters and oils of mustard, used as initial material, can be obtained bythe known processes. By treatment of primary or secondary aliphatic,aliphaticaromatic, aromatic, heterocyclic, araliphatic amines such asaniline, toluidines, Xylidines, trifluoromethylsubstituted anilines suchas 1- amino 4 3 trifiuoromethylbenzene, 1 amino 4-trifluoromethylbenzene, 1 amino 2 trifluoromethylbenzene,1-aminoe2-methoxy-5-trifluoromethylbenzene, l-amino -,2- chloro -5-trifluoromethylbenzene, l-amino 2 nitro 4 trifluoromethylbenze, l-amino3,5 bis-trifiuoromethylbenzene, 1=amino-2,5abis-trifluoromethylbenzene,4 fluoro methyl 2 aminophenylmethylsulphone, 4-aminoorZ-amino-trifiuoromethylsulphonbenzene (prepared by reduction of poro-nitrotrifiuoromethylsulphonbenzene SP 210 338) 2,4 dichlorophenyl -6-amino 1- trifluoromethylsulphone (prepared by reduction of 2,4-dichlorophenyl 6 nitro 1 trifiuoromethylsulphone), 2-methyl-4-1chlorophenyl -6- aminol-trifiuoromethylsulphone (prepared by reductionof 2-.methyl 4 chlorophenyl 6 nitro-1- trifiuoromethylsulphone SP 211777) 4-methylphenyl 6 amino 1 trifluoromethylsulphone (prepared byreduction of 4-methylphenyl-6- nitro-1-trifluoromethylsulphone SP 2117'74), 4 chloroaniline, 2 chloroaniline, 3,4 dichloroaniline, 2,5dichloraniline, 2,4 dichloroaniline, 4 chloro 2 aminophenylmethylsulphone (SP 172 361), 5,8 dichloro 1 naphthylamine, 3 chloro 4methyl 6 methox-y aniline, 3-chloro-4-methyl-6-ethoxyaniline,3,4-dichloro- G-methoxyaniline, 4-nitraniline, ethylaniline, 4'.- laurylaniline, laurylphenylamine, diphenylamine, 2 aminobenzothiazole, 3,4,5trichlorC aniline, 2,4,5 -trichloraniline, laurylamine, u..-dodecylbenzylamine, 4 amino 1,1' diphenyl ether,2-amino-1,1'-diphenylether, 4-amino-l,l'

diphenylsulfide, 4-amino-4'-chloro-1,1'-diphenylether,4-amino-2-chlorodiphenylether, 4-amino- 2',4 dichloro 1,1 diphenylether,4 amino- 3,4' dichloro 1,1 diphenylether, 4 amino- 3' methyl 4 chloro1,1' diphenylether, 4-amino-3, 5'-dimethyl-4-chloro-1,1'-diphenylether,4-amino-4'-methyl1',1-diphenylether, 4- amino 4' amyl 1,1'diphenylether, 2-chloro- 4-amino-4'-chloro-1,1-diphenylether,2-chloroii-amino 3', 4' dichloro 1,1 diphenylether, 2-chloro 4 amino 4chloro 1,1 diphenylsulphide, 2-amino -4- chloro 1,1 diphenylsulphide, 2amino -3', 4'- dichloro -1,ldiphenylsulphide, 2-amino -'4,4- dichloro-1,-1'- diphenylether, 2-amino 4,4 dichloro 1,1 diphenylsulphide, 2amino 4 chloro 4 methyl -1,1'- diphenylether, 2-amino 4,3, 4 trichloro1,1- diphenylether, 2-amino-3'-methyl-4,4'-dichloro- 1,1 diphenylether,2 amino 4 chloro 4- trifluoromethyl 1,1 diphenylether, 2 amino- 4'methyl 4 trifluoromethyl 1,1 diphenylether, 2 amino 4' amyl 4trifiuoromethyl- 1,1 diphenylether, 2 amino 4 chloro 4-trifiuoromethy1-l,l'-dipheny1sulphide, 4-.amino- 4 chlorodiphenyl, 4amino 4' acetylaminodiphenyl, 2 amino 3' trifluoromethyl 1,1.-diphenylether, 2 amino 4 chloro 3" trifiuoromethyl 1,1 diphenylether, 4chloro 3'- amino diphenylenoxide, 4 amino 4 chloro- 2-trifiuoromethyl1,1 diphenylether, 4-amino- 4-methyl 2 trifiuoromethyl 1,1 di eny ether,4 amino 3', 4 dichloro -'2 trifluoromethyl-1,1-diphenylether,4-amino-4'-chloro- 2 trifluoromethyl 1,1 diphenylsulphide, 4 amino 3methyl 4 chloro 2 tri fluoromethyl-l,1-diphenylether, 4-amino- 24'-dichloro -2- trifluoromethyl .-1,1'- diphenylether etc. with phosgenethe carbamic acid chlorides are formed. By suitable reactions known perse the latter which are obtained from the correponding primary aminesare easily transformed into the isocyanic acid esters.

Disguised isocyanates i. e. substances which generate isocyanate as forexample water soluble adducts of isocyanate and bisulfite and the likereact in a similar manner.

By reaction of alcohols, e. g. methylol, ethylol, benzylalcohol orphenols as halogen substituted phenols or trifiuoromethylphenol,nitrophenol and the like, with phosgene in the presence of tertiarybases one obtains the reactive chlorocarbonic acid esters. On the otherhand isothiocyanates may be produced by known processes from amines.

The products obtained by transposition of thiocyanicacid esters haveproved to be oi special value and availability. Benzylhalogenide andnuclearly halogenated benzylhalogenides but also saturated orunsaturated alkylhalides are suitable starting materials.

Further acylating agents for the aromatic or heterocyclic aminosulphonicacids are the cyanuric acid or their reactive derivatives or productsreacting like these. Examples therefor are cyanuric chloride, cyanuricbromide, thioalkylp triazine derivatives, chlorodiaminotriazine etc.Thereby the aromatic or heterocyclic aminosulhonic acids may react withthe reactive triazine derivatives one but preferably twice whereby theremaining last reactive member of the triazine radical may remain assuch or may "be reacted with compounds containing a hydrogen atqm pableof reaction, such as ammonia, a id alcoho s al ohola es 0r enolates andanorgani c alk s ercaptanes. The sequence of the introduction of allthese reactants is insignificant for the efiicacy of said products ofcondensation, provided that they contain a trifluoromethylgroup, asulphonic acid group, and a diphenylradical or a diphenyloxide-,diphenylsulphide-, 'diphenylsulfonide-, diphenylsulphone-,diphenylmethane-, diphenyl-carbamideor a stilbene radical, respectively.If the products are insoluble or difficultly soluble in water they maybe made water-so1uble by sulphonation. These novel products ofcondensation are obtained by know processes see for example Chem.Zentralblatt 1925 II S. 775-78l. As fixing agents for the hydrohalidesone may use sodium acetate, alkalicarbonate or alkalialcoholate.

All these watersoluble acylated condensation products contain noauxochromic groups or substituents which would impart any colour to thecompound.

By subsequent halogenation in manner known per se they may betransformed into halogenated or higher halogenated acylated compoundsSuitable aromatic or heterocyclic amino-sulfonic acids are the sulfonicacids of the aminodiphenyls, the aminodiphenylethers, theaminodiphenylsulphides, the amino-diphenylsulphoxides, theaminodiphenylsulphones, the aminodiphenylurethanes, theaminodiphenylcarbamides or aminodiphenylstilbenes, or theaminodiphenylthiocarbamides, the aminodiphenylketones, the aniline,anisidine, halogenated anilines and the like. Especially suited arealkyland/or halogensubstituted derivatives of the above mentionedaminosulphonic acids, like benzidine monosulphonic acid,4-methyl-2'-arnino-l,l-diphenylether 4' sulphonic acid, 4 methyl 4-amino-l,1'-diphenylether-2-sulphonic acid, 2- amino-1,1-diphenylether-2-or 4'-sulphonic acid, 3,4-dimethyl-4'-amino-1,l'-diphenylether-2-sulphonic acid, 4-methylor 3,4-di1nethyl-2- amino-l ,l-diphenylsulphide-4 -sulphonic acid, 4 methylor 3,4 dimethyl 2 amino1,1- diphenylsulphoxide 4 sulphonic acid, 3,4 dimethyl 4' amino 1,1diphenylsulphone-2'- sulphonic acid, 4-amino-4'-tert.amy11,1-diphenylether-Z-sulphonic acid, 4-amino-3', 5'-climethyl 1,1diphenylether 2 sulphonic acid, 3 methyl 4 amino 1,1 diphenylether 2-sulphonic acid, 4-amino-l,1'-diphenylether-2'- sulphonic acid,3-trifluoromethyl-2-amino-1,1- diphenylether 4 sulphonic acid, 3triiiuoromethyl 4' amino 1,1 diphenylether 2- sulphonic acid,4-trifluoromethyl-4'-methyl-2- amino 1,1 diphenylether 2' sulphonicacid, 4-trifluoromethyl-4-tert.amyl-2-amino-l,1'-diphenylether-2-sulphonic acid, 4-trifiuoromethyl-4-butyl-2-amino-1,1-diphenylether-2-sulphonic acid,4-trifiuoromethyl-4-chloro-2-amino-l,l'- diphenylether 2' sulphonicacid, 4 trifiuoromethyl 4' methoxy 2 amino 1,1 diphenylether-2-sulphonicacid, 4-amino-2-trifluoromethyl 4' methyl 1,1 diphenylether- 2-sulphonicacid, 4-amino-2-trifluoromethyl4'-chloro-l,l'-diphenylether-2'-sulphonic acid, 4,4- dichloro 2 amino 1,1diphenylether 2'- sulphonic acid,4-chloro-4'-amino1,l'-diphenylether-2'-su1phonic acid,4,2'-dichloro-4'-amino- 1,1-diphenylether-2-sulphonic acid,4-trifluoromethyl 3',4 dichloro 2 amino 1,1 diphenylether-2-sulphonicacid, 4,4',5trichloro- -2-amino-l,l-diphenylether-2'-sulphonic acid, 3methyl 4 chloro 4' amino 1,1 diphenylether-2-sulphonic acid,3,4-dichloro-4- amino-1,1'-diphenylsulphide-2'-sulphonic acid, 3,4dichloro 2 amino 1,1 diphenylether- 4 sulphonic acid, 4 chloro 4 amino1,1- diphenyl-sulphoxide-2'-sulphonic acid, 4-chloro-4amino-1,1-diphenylsulphone 2' sulphonic acid, 4,4 dichloro 2 amino 1,1diphenylmethane-2-sulphonic acid, 3'-aminobenzoyl-3,4-

dichloroanilide-6-sulphonic' acid, amino-stilbenedisulphonic acid etc.Examples for the class of heterocyclic aminosulphonic acids areaminobenzothiazol-sulphonic acid, 3 amino phenothioxine-x-sulphonicacid, 4-chloro-3'-amino-diphenyleneoxide-x-sulphonic acid. The'aromatichalogen substituted aminosulphonic acids of the benzene series which maybe condensed with the carbonic acid derivatives of theaminodiphenylethers or aminodiphenylsulphides are for example:4-ch1oroaniline-6-sulphonicacid, 4-bromoaniline-S-sulphonic acid,3,4-dichloroaniline- 6-sulphonic acid, 2,6-dichloroaniline-4-sulphonicacid, 2-chloroaniline-4-su1phonic acid, 2-chloro-4-toluidine-5-sulphonic acid, l-amino-3-trifiuoromethylbenzene-4-su1phonic acid,1-amino-4-trifiuoromethylbenzene-2-sulphonic acid, l-amino- 4trifluoromethylbenzene 2 sulphonic acid, 1 amino 2trifluoromethylbenzene 4 sulphonic acid,1-amino-2-chloro-5-trifiuoromethylbenzene-4-sulphonic acid,1-amino-2,4-dichloro- 3 trifluoromethylbenzene '6 sulphonic acid, 1amino 2,5 dichloro 3 trifluoromethylbenzene-4-sulphonic acid,l-amino-2-bromo-5- trifluoromethylbenzene 4 sulphonic acid, 1- amino 4chloro 2 trifiuoromethylbenzene-G- sulphonic acid,1-amino-4-chloro-3-trifluoromethylbenzene 6 sulphonic acid, 1 amino-2methoxy 5 triiiuoromethylbenzene 4 sulphonic acid, 1 amino 4-methoxy 5trifiuoromethylbenzene-2-sulphonic acid, l-amino- 2 ethoxy 5trifluoromethylbenzene 4 sulphonic acid,1-amino-3,5-bis-trifluoromethylben1 zene 4 sulphonic acid, 1 amino 3trifluoromethylbenzene 4 methylsulphone 6- sulphonic acid and the like.

If the substituents are properly chosen one may build up products withone or more sulphonic acid groups. If for example phosgene,

" thiophosgene or carbondisulphide are reacted with aminodiphenylethersulphonic acids containing trifluoromethyl groups, carbamidesorthiocarbamides with two sulphonic acid groups are formed. On the otherhand the reaction between the cited carbamic acid chlorides andaminosulphonic acids gives carbamides with one sulphonic acid group. Thetrifiuoromethyl group may be in one or both of the reacting components.Similarly in the condensation with cyanurchloride it is possible toobtain symmetric or asymmetric condensation products having one or moresulphonic acid groups by choosing suitable components. In this case theproducts containing two molecules of aminodiphenylethersulphonic acidsare of special importance.

It is known from the U. S. Patent No. 2,363,042 to condense3,4-dichloroaniline-fi-sulphonic acid with halogensubstituted aromaticcarbamic acid derivatives. These compounds did not find in dustrial useand their efi'icacy is inferior to the product containingtrifluoromethyl groups.

The acylated aminoarylsulphonic acids mentioned above are extremelysuited for protecting of wool, feathers, furs, hairs, paper, textiles,leather, natural or synthetic fibers or articles containing saidproducts against moths and other textile pests. Of special interest istheir pronounced washand fulling-proofness. By suitable substitutionthey may also be useful as disinfectants, as bactericides, fungicidesand in 7 secticides, as excellent mercury-free seed preserving agentsand as textile adjuvants.

Example 1 1 mol 4-methy1-4-trifluoromethyl-2'-amino-1,1-diphenylether-2-sulphonic acid, prepared by condensation of 1-chloro-2-nitro-4-trifluoromethylbenzene and p-cresol, sulphonation andreduction. of the product of condensation is suspended in dry pyridine.To this suspension is added drop by drop a molecular amount ofpalmkerneloil fatty acid chloride (mol. w. 220) while stirring at atemperature of 20-35 C. until a sample contains no free amino acid. Themixture is then made alkaline with sodium carbonate, the pyridine blownon with steam and the remaining solution acidified with hydrochloricacid after having been cooled. The precipitated mass is washed withpetrol-ether to remove an excess of palmkerneloil fatty acid, wherebythe 4 methyl 4' trifluoromethyl-2- laurolyamino-Ll-dipheny-lether 2sulphonicacid of the following formula is obtained in a pure state:

( OsH Instead of the 4-methyl-4-trifluoromethyl-2"-am-ino-1,1'-diphenylether 2 sulphonic acid one may use the i-tert.amyl-4-trifiuoromethyl- 2 -aminol,1-diphenylether 2 sulphonic acid, the4-methoxy-4-trifluoromethyl-2-amino-1,1'-diphenylether-Z-sulphonic-acid, the 4-chloro-4'- trifluoromethyl 2'amino 1,1 diphenylether -2-sulphonic acid, the 4-buty1-4'-trifiuoromethyl-2 -amino-1,1 -diphenylether-2-sulphonic acid, the 4 chloro 5methyl-4'-trifluoromethyl-2- amino-1,1-diphenylether-2-sulphonic acid,the 4,6- dichloro-4'-trifiuoromethyl-2-arnino 1,1-diphenylether-2-sulphonic acid, the 4-tert.amylfi-chloro-et'-trifiuoromethyl 2 amino-l,l-diphenylether-Z-sulphonicacid, the 4,5-dichloro- 4' trifluoromethyl-2"-amino-l,1 -diphenylether2i-sulphonic acid, the4-chloro-4'-amino-2-trifluorom-ethyl-Ll-diphenylether 2 sulphonic acid,the 4-methy1-4' -amino-2 -trifluoromethyl 1 ,1'-di-phenylether 2sulphonic acid, the 4- chloro-5-methyl-4-amino 2' trifluoromethyl-1,1-diphenylether-2-sulphonic acid. Theseamino-trifluoromethyl-diphenylether-sulphonic acids are prepared: byknown methods from phenols and 1 chloro-Z-nitro-4-trifiuoromethylbenzeneor 1-chloro-2 -trifiuoromethyl- -4 nitrobenzene; whereby the firstformed nitrodiphenyletheris sulphonated and reduced.

Example 2 a. Molecular amounts of4-ch1or0-4K-trifiuoromethyl-2"-amino-1,1-diphenylether-Z-sulphonic acid,prepared by condensation of p-chlorophenol with1--chloro2-nitro-4-trifluoromethylbenzene, sulphonat-ion and reduction.of the product of condensation: are dissolved in. water with addition ofa sodium carbonate solution and stirred 5 hours at 209-25? (3.. with3,4-dichlorobenzeylchloride whereupon no. free amino group isdetectable. The weakly alkaline solution is cooled andmixed' with brine,whereby the prodnot of condensation. is. precipitated in resinous form.It is. separated and dried in a vacuum to 8 obtain a bright watersoluble powder. It hasv the following formula Instead of3,4-dichlorobenzoylchloride one may also use 2,4-dichlor0benzoylchlorideor 2,5- dichlorobenzoylchloride.

b. By condensation of 4-tert.amyl-4-trifluoromethyl-2'-amino-1,1diphenylether 2 sulphonic acid with3,4dichlorobenzoyl-ch1oride the following compound is obtained:

( SOSH 01 Example 3 Molecular amounts of 4-amino-4'-methyl-1,1'-diphenylether-2-sulphonic acids and 3-tri'fluoromethyl-benzoylchlorideare subjected to the reaction of Schotten-Baumann. The weakly alkalinesolution is mixed with a sodium chloride solution to precipitate theproduct of condensation. The latter is dried in a vacuum and extractedwith absolute alcohol. After evaporation of the alcohol a brittle mass,which is readily pulverised is obtained; it is soluble in water. Theproduct has the formula CHFOWQWECOQ Instead of4-amino-4-methy1-1,1-diphenylether-Z-sulphonic acid one may use otheraminodiphenylethersulphonic acids as for example: 4- amino 4' -ch1oro-5-methyl- 1,1 -diphenylether- 2- sulphonic acid, 4 amino-4-tert. amyl-6'-chloro-1-,1-diphenylether-2-sulphonic acid, 4.- amino 2',425-trich1oro-1,1-diphenylether-2- ,sulphonic acid, 2amino-4',5-dieh1oro-l,1-diphenyletherl-sulphonic acid,2-amino-4Q5-dichloro 5 methyl 1,1 diphenylether 4-su'lphonic acid, 4--amino-2'-chloro-1,l-dipheny1- ether-2-suiphonic acid,4-amino-4',6-dichl'oro- 1,1-diphenylether-2-sulphonic acid, 2-amino- 4Z6dichloro 1,1 diphenylether-4-sulphonic acid, 4amino-4'-ch1oro-1,1-diphenylether-2.- sulphonic acid,2-amino-4'-chloro-1,1-diphenyletheri-sulphonic acid,2-amino-4.--chloro-5- methyl-1,1-diphenylether-4-sulphonic acid, 4&-amino. 4,5-dichloro-1,l-diphenylether-2-sulphonic acid,4-amino-4'-chloro-3',5-dimethyl- 1,1-diphenylether-2-sulphonic acid,2-amino-4-- chloro 3,5-dimethyll,l-diphenylether-4-sulphonic acid,4-amino4'-chloro-3'-methyl-6-isopropyl-1,1'-diphenylether-2-sulphonicacid, 2'- amino 4'amyl-6-chloro-1,1-diphenylether-4rsulphonic acid,4-amino-2-methyl-5'-isopropyl- 1,1-diphenylether-2sulphonic acid etc.

The diphenylether sulphonic acids are prepared in a manner known per seby condensation of 0- or p-chloronitrobenzenesulphonic acid with thecorresponding phenols and subsequent reduction.

Examples! /2 molsodiumsalt of 4-chloro-4'-trifluoromethyl2'-amino-1,1'diphenylether sulphonic acid is dissolved in water and thesolution cooled to 10 C. The 4-chlorophenylacetochloride is added dropby drop in an amount slightly exceeding the calculated amount andstirred without cooling until a sample shows no diazoreaction. Ifdesired a little more of the acylating agent is added. The reactionmixture is then neutralised with sodium carbonate and the product ofcondensation is precipitated with sodium chloride solution. It forms aresinous mass which is dried in a vacuum. Thereafter the product may beeasily pulverised and is soluble in water. It has the following formula:

, Instead of 4-chlorophenylacetochloride one may use the reactivederivatives of cinnamic acid as 4-chloro-cinnamic acid chloride,2-chloro-cinnamic acid chloride, 4-methoxy-ci'nnamic acid chloride.

Instead of 4 chloro 4-trifluoromethyl-2'-amino-1,1'diphenylether-2sulphonic acid, one may use other diphenylethersulphonic acids containing trifluoromethyl groups, for example thosementioned in Example 1.

Example 5 lowing formula:

(6) som SOaH Cl C F: FaC 0 Cl Instead of succinic acid chloride one mayuse diethylmalonic acid dichloride, glutaric acid dichloride, adipicacid dichloride and terephthalic acid dichloride.

Example 6 U methyl 4' trifluoromethyl 2' aminol,1' diphenylether 2sulphonic acid obtained by condensation of m-cresol with 1-chloro-2-nitro-4trifluoromethylbenzene and subsequent sulphonation and reductionis reacted in pyridine with palmkernelfatty acid chloride in' a mannerknown per se. /20 mol of. this product of condensation is dissolved in200 parts by volume of water with the calculated amount of sodiumcarbonate. Chlorine is introduced into this solution having regard thatthe reaction of the solution is held always slightly alkaline by addingdropwise sodium hydroxide solution. After about 2 hours the halogenatedcompound is precipitated with hydrochloric acid, extracted with ether,washed and dried. When the ether is distilled oil a pasty residueremains. In form of its sodium salt the new compound is a bright powderwhich 10 is readily soluble in water and gives foaming solutions. It hasprobably the following constitution:

(7) SO H I OH; NED-C OC11H23 Example 7 suction and dried in vacuum. Ithas the following formula:

SEO3N3. a

Instead of 3,4-dichloroaniline-6sulphonic acid one may use3,4dimethylaniline-6sulphonic acid or 4chloroaniline-d-sulphonic acid ormetanilic acid. The 3fiuoromethyl-1,1'-diphenylether-4'- carboxylic acidis obtained by hydrolysation of 3-trifluoromethyl-4-cyano-1,1-diphenylether. The latter is prepared byknown methods from diazotised 3trifiuoromethyl-4-amino-1,1-diphenylether.

Example 8 6 mol 3trifiuoroaniline-6sulphonic acid are dispersed in partsby vol. pyridine and stirred with mol4-chloro-1,1-diphenylether-4'-carboxylic acid chloride at roomtemperature for a period of 10 hours. Then the mixture is distilled withsteam treated with sodium bicarbonate solution cooked with hot water andfiltered. The product of condensation separates from the hot filtrate incrystalline form. It is filtered and dried in vacuum. Its formula is asfollows:

I SOaNa Instead of 3-fiuoromethyl-6aniline-sulphonic acid one may use4-chloro3-trifiuoromethylaniline-g-6-sulphonic acid. Instead of4chloro-1,1'- diphenylether-4'carboxylic acid chlorides one may use2',4-dichloro-1,1-diphenylether-4'-carboxylic acid chloride,2,4-dichloro-1,1-diphenylether-4'-carboxylic acid chloride, 3-methyl-4-chloro 1,1 diphenylether 4 -'carboxylic acid chloride or bromide, 4,4dichloro 1,1- diphenylether 2 carboxylic acid chloride, 3,4- dichloro1,1 diphenylether 4 carboxylicacid chloride, 4 bromo 1,1 diphenylether-4'-carboxy1ic acid chloride, diphenylether-hoarboxylic acid chloride,4-methoxy1,1-diphenyl'- ether-4f-carboxylic acid chloride, diphenylenoxide-IS-carboxylic acid chloride, 4'-chloro-1,l'-d1-phenylsulphidei-carboxylic acid chloride, 3,3-dichloro-1,1-diphenylsulphide-4-carboxylic acid chloride,324-dichloro-1,1-diphenylsulphide-4- carboxylic acid chloride. In placeof the carboxylic-acid chlorides other acid derivatives capable ofreaction may be used.

Example 9 Instead of trifluoromethylaniline-fi-sulphonic acid one mayuse 4-chloro-3-trifluoromethylaniline-fi-sulphonic acid. Instead of4-chloro-1,1- diphenyletheri-sulphochloride one may use thediphenylether-l-sulphochloride, 2-chloro-1,1'-

diphenylether 4 sulphochloride, 2,4 dichloro- 1.1-diphenylether-4'-sulphochloride or 4'-chloro 3" methyl 1,1 diphenylether 4sulphochloricle.

Example 10 following constitution:

11 scan r m-so o1 or: Q

It is also possible to react another diphenyletheror diphenylsulphidesulphonic acid.

b. With 4', 4-dichloro-2-amino-l,1-diphenyl ether-2-sulphonic acid andl-trifiuoromethyl-Z- chlorobenzene-5-sulphonic acid for example theproduct. of the following formula is obtained.

0. With 4 methyl 4'-amino-l,1-diphenylether-Zf-sulphonic acid andl-trifiuoromethylbenzene-3-sulphochloride the following. product isobtained.

CHVQOONEPSOQ SIOBH or, Other aminodiphenylethersulphonic. acids may alsobe used.

Example 11 18 parts 4 methyl 4' trifiuoromethyl 2'-amino-1,l'-diphenylether-2-sulphonic acid are dissolved in water withthe necessary amount of 10% sodium carbonate. To this solution are given35 parts of crystallised sodium acetate and then phosgene at 4050 C. isfed into this solution until no free amine can'be detected in a sample.The solution is then neutralised, whereupon theN,N'-2,2-(4,4'-dimethy1-2, 2-disulpho-diphenoxy) 5,5di-trifluoromethyl-diphenylcarbamide separates out in form of a paste.This is isolated and dried to obtain a water solu ble powder,corresponding to the following formula:

(14) s'oaH HOaS Ga O CF. MQ G I NH C O NH Instead of phosgene one. mayalso use substances which deliver phosgene, like pyridine chlorocarbonyl(Fridl. 6 1162) perchloromethylformiat, hexachlorodimethylcarbonate orother similar substances. Instead of 4- methy1-4"-trifiuoromethyl 2'amino-l,l'-diphenylether-2- sulphonic acid one may use otherdiphenylethersulphonic acids containing trifiuoromethyl groups, forexample those mentioned in Example 1.

Example 12 45 parts 4-chloro-4-trifluoromethyl2' amino-1,1'-diphenyle.ther dissolved in 50 parts by volume of alcohol are mixedwith 50, parts by volume of carbon disulphide and 0.3 part by weightsulphur and heated during 6 hours with reflux. hydrogen sulphide escapesin great amounts. The so formed N,N-2,2'-(4, 4"- dichloro diphenoxy)5,5'-di-trifluoromethyldiphenyl-thiocarbamide is filtered by suction andwashed with a little amount of alcohol.

40 parts of this thiocarbamide are dissolved in 200 parts of sulphuricacid monohydrate at a temperature of 10 C., then slowly heated to 20 C.until a sample has become water soluble with sodium carbonate. Thesulphonated mass is poured on ice and salted out. The N",N'-2,2'- (4",4-dich1oro-2", 2'"-disulpho-diphenoxyfi 5,5 ditrifiuoromethyl) diphenylthiocarbamide has the formula:

(15) Son Hols 010000 F; F3OOC -G1 NH os 1 I Example 13 then heated forfurther three hours at a temperature of 160-165" C. and then cooled. Thereaction may also be accomplished in a suitable solvent like acetone,anisol etc. Thereby the carbamide is formed in substantially theoreticalyields. 40 parts of this N'-4'-(4"-chlorophenoxy) phenyl N3-trifiuoromethylphenylcarbamide are added to 200 parts by weight ofsulphuric acid monohydrate at 10 C. and cooled to -l C. At thistemperature 35 parts by weight of 25% oleum are added drop by drop whilevigorously stirring. The stirring is continued until a sample is solublein diluted alkali. The mixture is then poured on ice, the acidneutralised and the product precipitated with salt. 40 parts of awatersoluble product are obtained, which is probablyN-4'-(2"-sulpho-4-chlorophenoxy) phenylN-3-trifluoromethylphenylcarbamide with the following formula:

I SOaH CF:

Example 14 a. 23 parts 4-amyl-4'-amino-1,1'-diphenylether-2'-sulphonicacid are dissolved in 150 parts by volume of anhydrous pyridine. To thissolution is given the calculated quantity of3-trifluoromethyl-phenyl-carbamic acid chloride at a temperature of -15C. while stirring, whereupon stirring is continued for an hour at 4050C. The mixture is treated with 100 parts of 10% sodium carbonate andtreated with steam until the pryidine is distilled oif. Upon cooling aresinous product separates from the aqueous solution and is collectedand dissolved in 500 parts of hot water. The solution is filtered whilehot and the N'-4'-(4" amylphenoxy) 2'-sulphophenyl- N -3 trifiuoromethylphenyl carbamide precipitated as a resin with a small amount of brine.It is separated from the aqueous layer, dried in a vacuum whereupon itsolidifies into a glassy mass. The yield is quantitative and the productcorresponds to the following formula:

AmylQO @NH- 0 0 NH@ I SO H CF:

0. Instead of the 3-trifiuoromethylphenyl-carbamic acid chloride one mayuse for example 3-trifiuoromethyl--chlorophenyl-carbamic acid chloride,3-trifluoromethyl 6-chlorophenyl-carbamic acid chloride,4-trifluoromethylphenylcarbamic acid chloridesZ-trifiuoromethylmethylphenyl-carbamic acid chloride or3,5-bis-trifluoromethylphenyl-carbamic acid chloride. By condensation of2-amino-4,4'-dichloro-1,1-diphenylether-2'-sulphonic acid with3-trifluoromethyl-4-chlorophenyl-carbamic acid chloride the N 2'-(4"-chlor0 2"-sulphophenoxy) 5'- chlorophenylN-3-trifloromethyl-4-chlorophenyl-carbamide of the following formula isformed:

Example 15 solution. It corresponds to the following formula:

( OGH In place of 3,4 dichlorophenyl-isocyanate one may use 4chlorophenylisocyanate, 2-chlorophenylisocyanate, 3,4,5trichlorophenylisocyanate, 3-trifluoromethylisocyanate, 3 -trifluoromethyl-4-chlorophenyl-isocyanate, 2,5-dichlorophenyl-isocyanate, 2,4dichlorophenyl isocyanate, 2,4,5-trichlorophenyl-isocyanate,2-methoxy-4-methyl-5-chlorophenyl-isocyanate,3,4-dimethylphenyl-isocyanate or 2,4-dimethylphenylisocyanate. Insteadof 4-chloro 4 trifiuoromethyl-2'-amino -1,1-diphenylether-2-sulphonicacid other amin'odiphenylether sulphonic acids containingtrifluoromethyl-groups, as specified in Example 1, may be used.

b. From 4-methyl-4'-trifluoromethyl2'-amino-l,1-diphenylether-2-sulphonic acid and 3-trifluoromethylphenylisocyanate the N'-2'-(4"- methyl-2"-sulphophenoxy)5' trifiuoromethylphenyl N-3 -trifluoromethylphenylcarbamide isobtained, which corresponds to the following formula:

0. Or from 4-tert. amyl-4'-trifluoromethyl-2'-amino-1,1-diphenylether-2-sulphonic acid and3-trifiuoromethylphenyl-isocyanate, the N 2'- (4"-tert. amyl2"-su1phophenoxy) -5-trifluoromethylphenyl N-3trifluoromethylphenylcarb- '15 amide is obtained which corresponds tothe following formula:

o F; Example 16 15 parts 3,4-dimethylaniline-fi-sulphonie acid aredissolved in 100 parts dry pyridine. To this solution the equivalentamount of 3-trifluoromethyl 6 (4' tert. amylphenoxy) phenylcarbamic acidchloride, prepared from 4-trifluoromethyl-1 -amyl-2-amino- 1 ,1-diphenylether and phosgene in a manner known per se, is added slowlywhile stirring at a temperature of -10 C. Then stirring is continued fora further hour at 4050 C. whereupon the solution is treated with aqueousbicarbonate solution and the pyridine blown off with steam. The residueis taken up in hot water, filtered and the clear filtrate admixed withbrine in order to separate N -3,4 dimethyl-G-sulphophenyl N'-2'-(4"-tert. amylphenoxy)- 5 trifluoromethylphenylcarbamide. It isdried in a vacuum and forms a brittle mass, which when pulverised issoluble in warm water. The carbamide has the following formula:

cnatksoan FsC-QOOCsHn NHC O--NH Example 17 a. To an aqueous emulsion ofmol 4,4-dichloro-2'-sulpho 1,1-diphenylether 2-0-phenyl-urethane thecalculated amount plus excess 3-trifluoromethyl-4-chloroaniline areadded and heated several hours on the boiling waterbath. The unreacted3-trifiuoromethyl-4-chloroaniline is then distilled off with steam, theresidue saturated with sodium chloride, the aqueous solution separatedfrom the precipitated oil. The latter is dissolved in a small amount ofwater, whereby the mixed carbamide becomes gradually crystalline. Theproduct is filtered by suction and dried. The N'-2-(4-chloro-2"-sulphophenoxy) -5'-chlorophenylN-S-trifluoromethyl-4-chlorophenyl-carbamide is obtained in good yields.Its composition and properties correspond to the product obtainedaccording to Example 140.

I aH b. By corresponding reaction of 4-chloro-4'- trifluoromethyl 2sulpho-1,1' diphenylether- 2-O-phenylurethane with 3,4- dichloroanilinethe N'-2-(4-chloro 2 sulphophenoxy) -5- trifluoromethylphenyl N 3,4dichlorophenylcarbamide corresponding to the product of Example l5a. isobtained.

'16 0. Reaction of 4,4-dichloro-2'-sulpho-1,1diphenylether-Z-O-phenylurethane with 4-trifluoromethylaniline givesN9-2' (4' '-ch1oro-2"- sulphophenoxy) 5'-chlorophenyl-N-4trifluoromethyl-phenylcarbamide (1. Reaction of 3',4"-dichloro 2sulpho-l,l'-

' diphenylsulphide-4-O-phenylurethane with 3- trifiuoromethylanilineproduces N A (3 ,4 dichlorophenylsulphide) 5-sulphophenyl-N-3-trifiuoromethylphenylcarb amide l l 01 303B 0 F3 SO H f. Reaction of4,4'-dich1oro-2'-sulpho 1,1- diphenyImethaneeZ-O-phenylurethane with 3-trifiuoromethyl-4-chloroaniline gives N -2' (4 chloro-2"-sulphobenzyl) 5chloropheny1-N-3- trifluoromethyl-4-chlorophenylcarbamide 9. Reaction of4,5'-dichloro-4-sulpho-1,1'- diphenylether-2-O-phenylurethane with4-trifiuoromethylaniline gives N-2- (3' ',4' dichlorophenyl) -5-sulphophenyl-N-4-trifluoromethylphenylcarbamide:

h. Reaction of 4-tert. amyl-2'-sulpho-1,1'-diphenylether 4-Ophenylurethane with 4-trifluoromethylaniline gives N-4'-(4-tert.amylphenoxy) 5 -sulphophenyl-N-4-trifluoromethylphenylcarbamide:

COOONH-CO-NHOCIM OH: 02115 g Example 18 (32) SOQH It possesses the sameproperties and constitution as the carbamide of Example 1511.

Example 19 mol p-chlorobenzoic acid chloroamide (prepared byintroduction of an equivalent amount of chlorine in an aqueoussuspension of p-chlorobenzamide at a temperature of 10-15 C. issuspended in water whereupon an equivalent amount of4-chloro-4'-trifluoromethyl-2-amino-1,1-diphenylether-2-sulphonic acidis added and vigorously stirred. At the same temperature the calculatedamount of 30% sodiumhydroxide is slowly added drop by drop, so that thetemperature does not exceed 20 0. Upon slow stirring the paste becomesmore and more consistent and the temperature rises slowly up to 30 C.and finally up to 40-45 C. When the temperature begins to fall themixture is heated for half an hour on the water-bath to 50-60 C. Aftercooling the mass is shaken with ether and the aqueous part boiled withwater, filtered while hot and mixed with brine. Thus the N-2-(4"- chloro2" sulphophenoxy) -5-trifiuoromethylphenyl-N-4-chlorophenylcarbamide isprecipitated.

20 gms. N-2'-(4"-chlorophenoxy)-5'-trifluoromethylphenylN-3,4-dichlorophenylcarbamide (prepared by condensation ofp-chlorophenolate and l-chloro-3-nitrotrifiuoromethylbenzene to form 4chloro-4'-trifiuoromethyl-2'-nitr0-1,1'- diphenylether, reduction andcondensation with 3,4-dichlorophenyl-isocyanate) are dissolved in 100gms. sulphuric acid monohydrate at a tem perature of 10 C. whereupon thecalculated amount of 25% oleum is slowly added at a temperature of l 0.The mixture is stirred until a sample is soluble in diluted alkalisolution. Then ice is added and the product salted out, as N 2'(4"-chloro-2"sulphophenoxy) -5'-trifluoromethylphenyl N3,4-diohlorophenyl carbamide.

Example 21 11.87 parts by weight well dried sodium salt of2-amino-4,4-'-dichloro-l,1'-diphenylether-2'- sulphonic acid aredissolved on the water-bath in 150 parts by volume of anhydrousacetonitrile. To this solution 10.45 parts by weight 3-trifluoromethyl 6(4-chlorophenoxy) -phenylisocyanic acid ester B. P. 0.08 mm./108 C.prepared from 2 amino--trifiuoromethyll-chloro-1,1'- diphenylether byknown methods, are added and heated several hours with reflux. Thereuponthe mixture is boiled with bone black and filtered. The solvent isevaporated in a vacuum and the product of condensation solidifies to abrittle foamy mass. In water it gives a clear solution. Yield 20 gms.The constitution is as follows:

(35) S O aNa NHC ONH Example 22 (36) S 0 :NE

CF NH CO The sulphonic acid used as starting material was prepared bygentle sulphonation of Z-amino- 4 chloro4-trifluoromethyl-1,1-diphenylether with oleum.

Emample 23 & mol of the sodium salt of 2-amino-4- methyl 4trifluoromethyl-l,1'-diphenylether- 2'-sulphonic acid obtained bysulphonation of 2- nitro-4 -methyl-4=-trifluoromethyl- 1,1-diphenylether with oleum and subsequent reduction according to themethod of Bchamp, are dissolved in 250 parts by volume of acetonitrileand treated with an equimolecular amount of3-trifluoromethyl-6-(p-cresoxy-) -phenylisocyanic acid ester. When theexothermic heat production ceases the mixture is heated for further 3hours on the water-bath with reflux whereupon the solvent is removed byvacuum distillation. The product of condensation gives clear solutionsin hot water; it corresponds to the following formula:

(37) sOaNB OHOO-OC F3 0 mQoGom ILIH c O NH If instead of3-trifluoromethyl-6-(p-cresoxy)- phenyl-isocyanic acid ester theB-trifluoromethyl- 6-(4-tert. amylphenoxy) -phenylisocyanicacid ester isused, the following product is obtained:

CH3 0 o F:

If 2- (3,5-dimethylphenoxy) -phenylisocyanate aeeaa'ie 19 is used; theproduct has the following constitution:

( CHa some I NH-CONH CH1 Example 24 c1 CF3 0 F3 0001 SOzNa ILIH 00 NHExample 25 By condensation of2-amino-4-chloro-4-trifiuoromethyl-Ll'-diphenylether 2' sulphonic acidwith 3-chl'oro-4- (4-chlorophenoxy) -phenylisocyanate B. P. 0.15 min/139C. according to Example 22. The following assymetric carbamide isobtained:

41 so aNa NHC O-NH 00-01 Example 26 If the sodium salt of4-amino-4-chloro-l,l"- diphenylether-2-sulphonic acid is condensed with3 -trifiuoromethyl-6- (4-chlorophenoxy) phenylisocyanate the followingwater soluble product of condensation is obtained:

S OaNa If the sodium salt of 2-amino-3', 4-dichloro-1,1-diphenylether-4-sulphonic acid is used instead of4-amino-4'-chloro-1,l'-diphenylether 2-sulphonic acid, the product hasthe following constitution & mol of the sodium salt of 4-amino-3,4-dichloro 1,1-diphenylsulphide-2-sulphonio acid is dissolved in hotanhydrous acetonitrile and treated with the corresponding quantity3'-trifluoromethyl- 6- (3 ,4 -dichlorophenoxy) phenylisocyanic acidester also dissolved in acetonitrile. When the exothermic heatproduction has faded Example 2'7 20 the mixture is heated for further lhours: with reflux, whereupon the solvent is distilled ofi a vacuum. Acondensation product corresponding to the following formula remains:

If e trifluorornethyl-4'-chloro-1,1-diphenylsulphide-2-isocyanic acidester the following product is obtained according to Example 27:

( iii-O s-ONH-o o NHC (i1 7 $0M s Example 28 The product of condensationof 2-amino-4- chloro-4 trifluoromethyl 1,1 diphenylether- 2'-sulphonicacid and 4-phenoxyphenyl-isocyanate is dissolved in glacial acetic acidand chlorine is fed into this solution during one hour. The product ofthe chlorination is precipitated by means of water containinghydrochloric acid in form of resinous semisolid mass. The sulphonic acidis transformed into its sodium salt which forms a bright powder clearlysoluble in hot water. Probably it has the following constitution:

(46 OaNa ILIH-C onwaOoQm Example 29 To an aqueous suspension of mol ofthe sodium salt of4,4-dichloro-2-sulpho-1v,1-diphenylether-Z-O-phenyl-urethane thecalculated amount plus an excess of 10% of 2-amino-4-trifluoromethyl-lf-chloro- 1,1 -diphenylether' are given and heated several hours on theboiling.

Water-bath. The mixture is then cooled and the unchanged amine extractedwith ether. The aqueous parts are boiled with an addition of water,treated with bone black and filtered while still hot. By addition ofsodium chloride solution the product separates in oily form. The aqueousliquor is separated from the oily product, which latter upon dryingsolidifies to a hard. mass soluble in hot water. The properties there ofare similar to those of Example 21.

Example 30 9.18 parts by weight 3-trifluoromethyl-4-chloroaniline-6-sulphonic acid are dissolved in. parts by volume of drypyridine and mixed. with a solution of 9.3 parts by weight S-chloro- 4(4' chlorophenoxy) phenyl I isocyanate in 25 parts by volume of drypyridine. The mixture is heated several. hours with reflux in awater-bath and then let stand over night. The

' product is then poured into 20 parts by volume of water, then ice isadded and the solution made congo-acid wfih concentrated hydrochloricacid. The precipitate is collected and dissolved in 5000 parts by weightof water and 12 parts by weight while hot, treated with bone black andOaNa If 3-chloro-6-(4' chlorophenoxy) phenyl 1- isocyanate is usedinstead of 3-chloro-4-(4'- chlorophenoxy) -phenyl-1-isocyanate thefollowing product is obtained:

CIGNMMH AOaNa Example 31 9.1 parts by weight of 3-trifluoromethyl-4-chloroaniline-6-sulphonic acid are dissolved in 60 parts by volume ofwarm anhydrous pyridine and mixed with a solution of 10.4 parts byweight of 2-(4' chlorophenoxy) 5 trifiuoromethylphenyl-l-isocyanate in25 parts by volume anhydrous pyridine. The mixture is heated severalhours on the water-bath and then let stand over night. The product ofcondensation is worked down in a manner similar to Example 30. Theproduct has the following formula:

(49) llFs 0 Fa AOaNa O Example 32 To an aqueous emulsion of mol3,4-dichloro- 6-sulpho 1 O phenylurethane the calculated amount plus anexcess of 10% of 2-amino-4-tri fiuoromethyl 4' chloro 1,1 diphenyletheris added and heated several hours on the boiling Water-bath. The mixtureis diluted with water (50) 01 (BIC-NH-C ONH some 0 Example 33 12 partsN'-2'- (3' '-methylphenoxy) -5-trifluoromethylphenyl N3,4-dichloro-6-sulphophenyl-carbamide obtained from 3-methy1-4'-trifluoromethyl 1,1 diphenylether 2' isocyanic acid ester and3,4-dichloroaniline-6-sulphonic acid, are dissolved in 60 parts byvolume glacial acetic acid and chlorine is introduced during one houruntil the solution is saturated; The chlorinated product is precipitatedwith hydrochloric acid containing water as a crumbly semi-solid mass.The sulphonic acid is transformed into the sodium salt and forms then abright powder. The constitution is probably as follows:

51) c1 CFs V I CH3 sO Na 0 01 O. Ewample 34 mol3trifluoromethyll-chloroaniline-6- sulphonic acid is dissolved in warmpyridine and mixed with a solution of the equivalent amount of(3',4-dichlorophenylsulphide)-phenyl-1-isocyanate in anhydrous pyridine.The mixture is heated several hours on the boiling water-bath and workeddown as shown in Example 30. The product has the following formula:

Ol-ONH-C O-NHO-SG-Cl Scam The 4- (3,4-dichlorophenylsulphide)-phenyll-isocyanate is obtained in the usual manner from 4amino-3',4-dichloro-1,1-diphenylsulphide with phosgene in benzenicsolution.

Ercample 35 a. 9.3 parts cyanurchloride are dissolved in parts by volumeof benzene and the solution cooled to 0 C. At this temperature asolution of 1.15 parts sodium in 80 parts by volume of methylalcohol isadded drop by drop with stirring. Sodium-chloride is precipitated. After30 minutes the mixture is heated to 30-40 0., whereupon a calculatedsolution of 4-chloro-4'-trifiuoromethyl 2' amino 1,1-diphenylether-2-sulphonic acid which was previously neutr'alised with sodium carbonatein 200 parts of water, is added while vigorously stirring. After 20-40minutes the acid which has been split off is neutralised with sodiumcarbonate. The mixture is then heated to -100 C. and the processrepeated with the same amount of said ether-acid. During the subsequentheating at 90100 'C. for 2 hours, whereby the formed acid is neutralisedwith sodium carbonate from time to time, the benzene and the excess ofmethylaloohol distill off. After cooling, the disulfonic acid isprecipitated with sodium chloride and dried. It forms a White powder,which is readily soluble in hot water. The product corresponds to thefollowing formula:

. O 0 i I 30311 H ns b. By similar condensation of 1 mol cyanurchloride,1 mol ethylate, 1 mol 4-amino-4'-chloro-1,l"-diphenylether-2-sulphonicacid and 1 mol 1 chloro 4' trifluoromethyl-2-amino-1,1-di- 23phenylether-Z-sulphonic acid; product is obtained:

the following o. By condensation of 1 mol cyanurchloride with 2 mol4-amino-4-chloro-3-methyl-1,1-diphenylether-2-sulphom'c acid and 1 mol3-trifluoromethylaniline the following product is obtained:

2&

Example 37 23 parts 4,4-dichloro-2amino-1,1'-diphenylether-2'-sulphoni'c acid are suspended in 100' d; Bycondensation of 1 mol cyanurchloride with two mol3-trifluoromethylaniline and 1- mol 4' chloro 3'methyli-amino-l,1-diphenyl ether-Z-sulphonic acid a condensation productof the following formula:

X g 0 3H N N C G v -Q Example 36 partsof the product of condensationobtained by reacting 1 mol cyanurchloride with 2. mol 3 methyl 4 amino1,1 diphenylether-Z-sulphonic acid and replacement of: thelastchlorine-atom in the cyanurring by 3-- trifluoromethylaniline aredissolved in 400 parts by volume glacial acetic acid and 200. parts byvolume concentrated hydrochloric acid. To this solution which is heatedto. a solution of 10 parts sodium chlorate in 100 parts water is addeddrop by drop within 5 hours. The precipitation is finally? completed byaddition of I000 parts. water. The product of chlorination workeddo-wn.as usual is soluble in water but more easily soluble in diluted sodiumcarbonate solution. Its properties and probably its constitutioncorrespond to Example 350.:

(57) CFI vacuum and forms an, easily pulverisable brittle mass;

( SO 3H- Example 38 a. Wool or wool containing material is boiled for 45minutes to one hour with 1.5% of the weight of the wool of.-methy1-4'-trifiu0romethyl-2. lauroylamino- 1.1- diphenylether-Z-suIphonic acid. (Example 1)., 35% sulphuric.

acid and 10 crystalline sodium sulphate,,whereupon the. material isrinsed and. dried. The treated material. is. moth proof.

5. W001 is treated at a temperature of. 60 C. during 45, minutes. with03-05% (calculated. on wool) N-2' (4' -';hloro-2' sulphophenoxy) -5.'chlorophenyl) N. 3-trifluoromethylr-4-chlorophenyl-carbamide (Example137.0.) and 10-20% crystalline sodium-sulphate, rinsed and dried. Thetreated material. is moth proof...

0. Noel or wool containing. material. is boiled for 45 minutes to onehour with 0.6% (calculated on wool) of the product of condensation de--scribed in Example 21, 34% sulphuric acid and 10% crystalline sodiumsulphate, whereupon the material is rinsed and dried. The so treatedproduct is moth-proof.

(1. W001 or wool containing material is boiled for 45 minutes to onehour with 0.8% (calculated on Wool) of the product of condensationdescribed in Example 30, 3-4% sulphuric acid and 10% crystalline sodiumsulphate. Thereupon the material is rinsed and dried. The so treatedproduct is moth proof.

e. Wool is treated at elevated temperature during 45 minutes to 1 hourwith 2% (calculated on wool) of a condensation product obtained from 1mol cyanurchloride, 2 mol 4'-chloro-3- methyl 4 amino 1,1 diphenylether2 sulphonic acid and 1 mol 3-trifiuoromethylaniline (Example 350), 4%sulphuric acid and 10 crystalline sodium sulphate. After rinsing anddrying the product is moth proof.

It will be seen that the great majority of the above compounds set forthare of the general form or, Q I

I I-( a H TBOzH where X is one of the group sulfur and oxygen and Rmonocyclic aromatic mono acyl radical. As shown in Compound 2 thehalogen may be in both R and the ether with CF3 in the ether. Compound 9shows no halogen in R but in the ether, while Compound 11 shows CF3 inboth the ether and R. Compound 16 shows halogen in the ether and only-CF'3 in R. It is thus seen that -CF3 and halogens, such as chlorine,may be located in either or both the ether and R. The CF% preferably ismeta to an N, but not necessarily, as in Compound 30, R includes etheracyls such as in Compounds 15, 41, 42 and other examples as shown. Thesulfonic acid group may be in R as in Compounds 8, 9, 41, 48 as well asin the ether portion.

What I claim is: 1. Trifluoromethyl substituted halogenatedamino-sulfonic acid compounds of the general formula H N R (halogen)TSOQH where n is a number from 1 to 4 and X is a member of the groupconsisting of oxygen and sulfur, and R is a monocyclic aromatic monoacyl radical, there being at least one -CF3 group in a nucleus in thecompound.

2. Trifluoromethyl substituted compounds of chlorinated sulfonic acidshaving the general formula where n is a number from 1 to 4 and R is aphenyl urea radical, said compounds containing at least onetrifluoromethyl group in a nucleus in the compound.

3. The compound 5. The compound soar:

Q01 omQo-Om NHO o-NH 6. The compound 4. The compound so H 01OIO-O-O-NH-o O-NHG-Cl HENRY MARTIN.

1. TRIFLUOROMETHYL SUBSTITUTED HALOGENATED AMINO-SULFONIC ACID COMPOUNDSOF THE GENERAL FORMULA